EP3157646B1 - Process for recovering an electrolyte salt - Google Patents
Process for recovering an electrolyte salt Download PDFInfo
- Publication number
- EP3157646B1 EP3157646B1 EP15729816.7A EP15729816A EP3157646B1 EP 3157646 B1 EP3157646 B1 EP 3157646B1 EP 15729816 A EP15729816 A EP 15729816A EP 3157646 B1 EP3157646 B1 EP 3157646B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal salt
- electrolyte
- solvent
- extraction
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000003839 salts Chemical class 0.000 title claims description 41
- 239000003792 electrolyte Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 28
- 238000000605 extraction Methods 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 20
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 159000000002 lithium salts Chemical group 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- DGTVXEHQMSJRPE-UHFFFAOYSA-N difluorophosphinic acid Chemical class OP(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021481 rutherfordium Inorganic materials 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- QQAHAGNPDBPSJP-UHFFFAOYSA-N 1,1,1,2,2,3,3,3-octachloropropane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl QQAHAGNPDBPSJP-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- -1 lithium salt anion Chemical class 0.000 description 3
- VTRRCXRVEQTTOE-UHFFFAOYSA-N 1-methylsulfinylethane Chemical compound CCS(C)=O VTRRCXRVEQTTOE-UHFFFAOYSA-N 0.000 description 2
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910006095 SO2F Inorganic materials 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical class [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0031—Chlorinated solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the present invention relates to a process for recovering a metal salt, in particular a lithium salt, contained in an electrolyte.
- Sulfonimide salts such as lithium bis(trifluoromethanesulfonyl)imide ((CF 3 SO 2 ) 2 NLi or LiTFSI), lithium bis(fluorosulfonyl)imide ((SO 2 F) 2 NLi or LiFSI) or lithium bis(perfluoroethanesulfonyl)imide ((C 2 F 5 SO 2 ) 2 NLi), are compounds of particular interest. They in particular have properties that make them valuable compounds for electronic applications that are demanding as regards purity and quality, for example the conduction and/or the dissipation of electronic charges in the battery or antistatic markets or in electrochromism. These compounds are in particular used in an electrolyte and are, in this case, in a matrix which may be a polymer, a gel or an organic solvent.
- application WO 2008/022415 describes a process for recovering lithium from the electrolyte of a lithium battery, according to which a spent battery is brought into contact with a solution of ethanol containing 5% of acetone and, after extraction of the lithium salt and chemical reaction thereof with various constituents of the medium, the lithium is recovered in the form of Li 2 CO 3 .
- the filtrate is then distilled so as to recover ethanol which may be used for a new extraction.
- only the lithium is recovered, and said lithium is in a modified chemical form which means that it cannot be re-used as it is in a lithium battery.
- Patent application FR 2 868 603 also describes a process for treating lithium-anode cells and batteries. Besides lithium, said document proposes only the recovery of the PF 6 anion.
- Patent application JP H05-017832 also provides a process for recovering the lithium contained in a lithium battery, but proposes no means for recovering the lithium salt anion.
- the objective of the present invention is to provide a process for recovering metal salts of electrolytes, especially lithium salts, in particular lithium sulfonimides and especially (CF 3 SO 2 ) 2 NLi, which causes little or no modification of the chemical nature of the metal salt and which also optionally makes it possible to recover the matrix of the electrolyte, whether it is in the form of a polymer, of a gel or of a solvent.
- the present invention relates to a process for recovering a metal salt of an electrolyte dissolved in a matrix, said process consisting in subjecting the electrolyte to a liquid extraction with water.
- metal salt is intended to mean an organic or inorganic salt of a metal, preferably of an alkali metal, in particular selected from: K, Li, Na or Cs. Lithium (Li) salts are particularly preferred.
- the metal salt may be selected from the group consisting of sulfonimides, perchlorates, sulfonates, difluorophosphates and mixtures thereof.
- sulfonimides having the formula (Rf 1 SO 2 )(Rf 2 SO 2 )NM b , M b representing an alkali metal, in particular selected from: K, Li, Na and Cs, Rf 1 and Rf 2 independently representing a fluorine atom or a group having from 1 to 10 carbon atoms, selected from fluoroalkyls, perfluoroalkyls and fluoroalkenyls.
- the Rf 1 and Rf 2 groups are independently selected from a fluorine atom or a group having from 1 to 5 carbon atoms, selected from fluoroalkyls, perfluoroalkyls and fluoroalkenyls.
- the metal salt may preferably be selected from lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide or lithium bis(perfluoroethanesulfonyl)imide, preferably lithium bis(trifluoromethanesulfonyl)imide.
- the metal salt may also be selected from LiClO 4 (lithium perchlorate) and LiOTf (lithium trifluoromethanesulfonate, also called lithium triflate).
- the metal salt may also be LiPO 2 F 2 (lithium difluorophosphate).
- the inorganic lithium salts may be selected from LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 or lithium borates and phosphates.
- the organic lithium salts are preferably selected from the fluoroalkyl variants of the above mentioned borates and phosphates, LiOTf (or lithium trifluoromethanesulfonate) or the above mentioned lithium sulfonimides, for example lithium bis(trifluoromethanesulfonyl)imide ((CF 3 SO 2 ) 2 NLi or LiTFSI), lithium bis(fluorosulfonyl)imide ((SO 2 F) 2 NLi or LiFSI) or lithium bis(perfluoroethanesulfonyl)imide ((C 2 F 5 SO 2 ) 2 NLi), in particular LiTFSI.
- electrolyte is intended to mean a medium containing ions which make it conductive, i.e. which allows an electric current to pass through.
- This medium may be solid or liquid.
- the ions are provided by the metal salt and said salt is dissolved in a non-conductive matrix which may be a polymer, a gel or an organic solvent.
- the extraction takes place by bringing into contact with water, preferably at atmospheric pressure and at a temperature of between 0 and 100°C, preferably between 20 and 60°C.
- the extraction solvent therefore contains at least water.
- An aqueous extraction solution is obtained, said solution containing at least a part of the metal salt.
- the matrix comprises a polymer or a gel in which the metal salt is dissolved, i.e. the metal salt has not chemically reacted with said matrix.
- the polymer contained in the matrix may be, for example, POE (polyethylene oxide) or a silicone oil.
- the gel contained in the matrix may be, for example, PAN (polyacrylamides), the PVDF (PolyVinylideneDiFluoride) homopolymer or a VDF (vinylidene fluoride) - HFP (hexafluoropropylene) copolymer.
- the polymer or the gel and, on the other hand, an aqueous solution containing at least a part of the metal salt are generally recovered.
- the polymer or the gel may optionally be re-used in the same application, as electrolyte, optionally after an appropriate treatment, involving, for example, drying.
- the matrix of the electrolyte comprises an organic solvent.
- the solution of the metal salt in the organic solvent i.e. the electrolyte
- this electrolyte may be successively or simultaneously subjected to a liquid extraction with water and with an organic extraction solvent which is water-immiscible.
- the steps of extraction with water and with the organic solvent may be carried out in any order.
- the aqueous extraction is carried out first.
- spent devices comprising an electrolyte are ground in the presence of water, for example under water or in the presence of a water mist, thereby making it possible to eliminate the heat emitted by the grinding and to avoid any risks of sparks.
- the organic solvent of the electrolyte should ideally have a good compromise between two antagonistic properties, namely: a high electric constant and a low boiling point (corresponding to a high fluidity). It is preferably at least one and preferably at least two solvent(s) selected from aliphatic sulfones, such as DMSO (dimethyl sulfoxide), DESO (diethyl sulfoxide), DPSO (dipropyl sulfoxide), EMS (ethylmethyl sulfoxide), or FEMS (fluroroethylmethyl sulfoxide); alkyl carbonates, such as PC (propyl carbonate), EC (ethyl carbonate) or DMC (dimethyl carbonate); nitriles, such as AdN (adiponitrile) and MGN (methylglutaronitrile); and GBL ( ⁇ -butyrolactone).
- aliphatic sulfones such as DMSO (dimethyl sulfoxide
- a mixture of at least two solvents generally makes it possible to more easily achieve the compromise of abovementioned properties. Good results have in particular been obtained with the EC/DMC mixture.
- the choice of the organic extraction solvent which is water-immiscible depends in particular on the solvent of the electrolyte, and those skilled in the art will be able to easily identify it on the basis of the solvent miscibility tables available in the literature. It should be noted that the extraction solvent may also be a mixture of solvents. Chlorinated solvents such as chloroform, dichloroethane and perchloroethylene are very suitable. Good results have been obtained with methylene chloride and/or chlorobenzene, in particular when the electrolyte comprises an EC/DMC mixture.
- the extraction step with the organic solvent is preferably carried out at ambient pressure and temperature.
- two liquid phases are present: an aqueous phase in which substantially all the metal salt is dissolved and an organic phase containing substantially all the organic solvent of the electrolyte and the organic extraction solvent.
- substantially is intended to mean at least 70%, preferably at least 80%, or even at least 90% of the initial amount present in the medium treated (either a spent, preferably ground, device, or an aqueous solution obtained by aqueous extraction thereof).
- these two phases are separated, for example by settling out or centrifugation.
- the two variants above are often combined since, industrially, a mixed stream of devices including both solid electrolytes and liquid electrolytes is generally treated and, consequently, in order to extract the metal salt therefrom, it is first necessary to carry out an extraction with water.
- the treated stream also comprises liquid electrolyte
- the liquid phase(s) resulting from the extraction with water is (are) then preferably subjected to an extraction with a water-immiscible organic solvent.
- one or each of these phases may be treated so as to recover therefrom respectively the metal salt and the solvent of the starting electrolyte.
- miscible with is intended to mean generally soluble at at least 5% by weight, or even at at least 10% by weight.
- miscible is intended to mean generally miscible at less than 5% by weight, preferably at less than 2% by weight.
- liquid extraction is intended to mean bringing into contact with water or the solvent in an amount and for a period sufficient to extract therefrom respectively a substantial amount of the solvent or of the metal salt, i.e. at least 70%, preferably at least 80%, or even at least 90% by volume of the initial amount present in the medium treated.
- the water or the solvent used may be substantially pure, preferably at least 70% by volume, preferably at least 80%, or even at least 90% pure.
- the ratio by volume of water or of liquid relative to the medium to be extracted may be between 20:80 and 80:20, preferably between 40:60 and 60:40.
- the duration of the bringing into contact may be, for example, at least 0.5 hour.
- the liquid extraction may be carried out in a single step or it may be carried out in several successive steps, i.e. it may be staged.
- the extraction with water is carried out in a single step.
- the extraction with the organic solvent where appropriate, is advantageously staged.
- at least 20% by volume of the organic solvent of the electrolyte is extracted in the first step, and as many steps as are necessary are preferably used to extract in total at least 90% of the solvent.
- the aqueous solution containing the metal salt is dried, for example by spray-drying, so as to extract therefrom the directly reusable metal salt.
- This variant is very suitable in the case of aqueous solutions which are sufficiently pure, i.e. which make it possible to obtain metal salts of which the purity is sufficient for the intended use (for example: re-use in an electrolyte).
- the metal salt is LiTFSI and the aqueous solution containing it is preferably first concentrated, for example by evaporation, distillation or lyophilization. This solution is then acidified so as to generate HTFSI, which is preferably first purified (for example by distillation, etc) and then brought into contact again with an aqueous solution of fresh LiOH or Li 2 CO 3 , so as to regenerate the LiTFSI.
- the aqueous extraction solution containing LiTFSI is acidified so as to generate HTFSI and LiHSO 4 which are isolated, and then the HTFSI is brought into contact with fresh LiOH or Li 2 CO 3 so as to regenerate the LiTFSI.
- the organic phase containing the solvent(s) of the electrolyte and the extraction solvent is treated so as to separate the solvents, for example by distillation.
- the solvents thus regenerated can optionally, as a result of additional treatment(s), also be re-used, preferably in the same application, i.e. respectively as electrolyte solvent and as extraction solvent.
- a synthetic electrolyte was obtained by incorporating LiTFSI (1M) into an EC/DMC mixture at 50% by volume of each of the two solvents.
- the resulting solution was extracted with an equivalent volume of methyl chloride, and then with an equivalent volume of water. Two phases, easy to separate by settling out, were obtained, the LiTFSI being at more than 95% by weight in the aqueous phase.
- a spent flexible battery weighing in total 34 g and comprising 2 g of LiTFSI in solution in an EC/DMC mixture was subjected to a single-step extraction with 600 g of water and 900 g of methylene chloride. Two phases, easy to separate by settling out, were obtained, and 1.8 g i.e. 90% of the LiTFSI in the aqueous phase were recovered.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1401375A FR3022695A1 (fr) | 2014-06-18 | 2014-06-18 | Procede de recuperation d'un sel d'electrolyte |
PCT/EP2015/063381 WO2015193261A1 (en) | 2014-06-18 | 2015-06-16 | Process for recovering an electrolyte salt |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3157646A1 EP3157646A1 (en) | 2017-04-26 |
EP3157646B1 true EP3157646B1 (en) | 2018-03-07 |
Family
ID=51610162
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15729816.7A Active EP3157646B1 (en) | 2014-06-18 | 2015-06-16 | Process for recovering an electrolyte salt |
Country Status (9)
Country | Link |
---|---|
US (1) | US10511068B2 (ja) |
EP (1) | EP3157646B1 (ja) |
JP (1) | JP6568117B2 (ja) |
KR (1) | KR102336872B1 (ja) |
CN (1) | CN106659947B (ja) |
CA (1) | CA2951594C (ja) |
FR (1) | FR3022695A1 (ja) |
TW (1) | TW201617122A (ja) |
WO (1) | WO2015193261A1 (ja) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3059994B1 (fr) * | 2016-12-08 | 2021-03-19 | Arkema France | Procede de sechage et de purification de lifsi |
FR3081724A1 (fr) * | 2018-06-01 | 2019-12-06 | Arkema France | Procede de purification du sel de lithium de bis(fluorosulfonyl)imide |
CN113060718A (zh) * | 2021-03-29 | 2021-07-02 | 兰州理工大学 | 废旧锂离子电池回收电解液制备二氟磷酸锂的方法 |
FR3121552A1 (fr) * | 2021-03-31 | 2022-10-07 | Arkema France | Procédé de recyclage de sels de lithium issus des batteries |
GB2609212A (en) | 2021-07-22 | 2023-02-01 | Mexichem Fluor Sa De Cv | Process |
KR20230046482A (ko) | 2021-09-30 | 2023-04-06 | 주식회사 천보 | 폐 이차전지의 전해질로부터 리튬염을 회수하는 방법 |
EP4273096A4 (en) * | 2022-01-29 | 2024-05-22 | Contemporary Amperex Technology Co., Limited | METHOD FOR RECOVERY OF LITHIUM BIS(FLUOROSULFONYL)IMIDE |
KR20230119926A (ko) | 2022-02-08 | 2023-08-16 | 주식회사 천보 | 폐 이차전지의 전해질로부터 리튬염을 회수하는 방법 |
KR20230139151A (ko) | 2022-03-25 | 2023-10-05 | 주식회사 천보 | 폐 이차전지의 전해질로부터 리튬염을 회수하는 방법 |
CN114759286A (zh) * | 2022-05-30 | 2022-07-15 | 清华大学深圳国际研究生院 | 一种锂离子电池废旧电解液的回收方法 |
CN114865134A (zh) * | 2022-05-31 | 2022-08-05 | 广东邦普循环科技有限公司 | 废锂离子电池电解液高效回收的方法 |
CN117246982A (zh) * | 2022-06-10 | 2023-12-19 | 时代思康新材料有限公司 | 双氟磺酰亚胺锂和提纯双氟磺酰亚胺锂的方法 |
CN115528338A (zh) * | 2022-09-16 | 2022-12-27 | 广东邦普循环科技有限公司 | 一种从锂离子电池电解液中回收锂的方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU624957A1 (ru) * | 1974-11-13 | 1978-09-25 | Aslanov Nikolaj N | Способ переработки медьсодержащего сплава |
JPH0517832A (ja) * | 1991-07-10 | 1993-01-26 | Daito Kagaku Kk | 廃リチウム電池からのリチウム回収方法 |
DE19743985A1 (de) | 1997-10-06 | 1999-04-08 | Merck Patent Gmbh | Verwendung von Tris(trifluoromethylsulfonyl)methan und dessen Alkali- und Erdalkalimetallsalzen als Katalysatoren bei C-C verknüpfenden Synthesen und das neue Mg-Salz von Tris(trifluoromethylsulfonyl)methan |
ATE502414T1 (de) * | 2002-01-09 | 2011-04-15 | Eco Bat Indiana Llc | Verfahren zum entfernen eines elektrolyts aus einer energiespeicherung und/oder einer umsetzungseinrichtung mit einem superkritischen fluid |
FR2868603B1 (fr) * | 2004-04-06 | 2006-07-14 | Recupyl Sa Sa | Procede de recyclage en melange de piles et batteries a base d'anode en lithium |
BRPI0603719A (pt) * | 2006-08-21 | 2008-04-08 | Lg Eletronics De Sao Paulo Ltd | processo para extração dos compostos de lìtio presentes nas baterias secundárias de ìons lìtio |
FR2924116B1 (fr) * | 2007-11-27 | 2010-02-26 | Rhodia Operations | Procede de preparation d'un sel de l'acide trifluoromethanesulfinique |
US8753594B1 (en) * | 2009-11-13 | 2014-06-17 | Simbol, Inc. | Sorbent for lithium extraction |
CA2767395C (en) * | 2009-07-07 | 2018-03-06 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
US9096502B2 (en) * | 2011-03-03 | 2015-08-04 | Nippon Soda Co., Ltd. | Production process for fluorosulfonylimide ammonium salt |
CN102179066B (zh) * | 2011-05-12 | 2013-10-16 | 中国科学院过程工程研究所 | 一种三相萃取分离同一种元素两种价态离子的方法 |
EP2410603A1 (en) * | 2011-08-31 | 2012-01-25 | Umicore SA | Recovery of compounds from Li-ion battery electrolyte |
JP5360328B1 (ja) * | 2013-06-04 | 2013-12-04 | Jointエンジニアリング株式会社 | 廃電解液から電解質用リチウム塩と有機溶媒を同時に回収する方法及びその装置 |
-
2014
- 2014-06-18 FR FR1401375A patent/FR3022695A1/fr not_active Withdrawn
-
2015
- 2015-06-16 CA CA2951594A patent/CA2951594C/en active Active
- 2015-06-16 US US15/318,119 patent/US10511068B2/en active Active
- 2015-06-16 EP EP15729816.7A patent/EP3157646B1/en active Active
- 2015-06-16 KR KR1020177001059A patent/KR102336872B1/ko active IP Right Grant
- 2015-06-16 CN CN201580044258.4A patent/CN106659947B/zh active Active
- 2015-06-16 JP JP2016573915A patent/JP6568117B2/ja active Active
- 2015-06-16 WO PCT/EP2015/063381 patent/WO2015193261A1/en active Application Filing
- 2015-06-18 TW TW104119873A patent/TW201617122A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
CA2951594C (en) | 2022-08-23 |
US10511068B2 (en) | 2019-12-17 |
CA2951594A1 (en) | 2015-12-23 |
TW201617122A (zh) | 2016-05-16 |
US20170110769A1 (en) | 2017-04-20 |
FR3022695A1 (fr) | 2015-12-25 |
KR20170018048A (ko) | 2017-02-15 |
CN106659947A (zh) | 2017-05-10 |
WO2015193261A1 (en) | 2015-12-23 |
JP2017525552A (ja) | 2017-09-07 |
CN106659947B (zh) | 2019-03-05 |
JP6568117B2 (ja) | 2019-08-28 |
KR102336872B1 (ko) | 2021-12-08 |
EP3157646A1 (en) | 2017-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3157646B1 (en) | Process for recovering an electrolyte salt | |
EP3733596B1 (en) | Alkali metal salt of fluorosulfonyl imide | |
US10316006B2 (en) | Heterocyclic ionic liquids | |
EP3231769B1 (en) | Manufacturing method for lithium difluorophosphate powder, and lithium difluorophosphate | |
KR102208181B1 (ko) | 비스(플루오로설포닐)이미드 알칼리 금속염의 제조방법 | |
KR20190002543A (ko) | 비스(플루오로술포닐)이미드 알칼리 금속염의 제조 방법 및 비스(플루오로술포닐)이미드 알칼리 금속염 조성물 | |
EP3045426B1 (en) | Granules or powder of disulfonylamide salt, and method for producing same | |
JP4972915B2 (ja) | 非水電解質電池 | |
JP2012531714A (ja) | 高電圧電解質 | |
EP2744753A1 (en) | Manufacture of mixtures comprising lipo2f2 and lipf6 | |
EP2855444B1 (fr) | Sel d'anions bicycliques aromatiques pour batteries li-ion | |
EP2819951A1 (de) | Leitsalz für lithium-basierte energiespeicher | |
KR20040030140A (ko) | 중합체 전해질 및 갈바니 전지에 있어서의 그 용도 | |
JP2000211916A (ja) | 六フッ化リン酸リチウムまたは四フッ化ホウ酸リチウムを含有する有機溶液の処理方法 | |
CN109369603A (zh) | 一种2-磺酸酯基-1,3-二碳酸酯化合物的制备方法 | |
DE19953051A1 (de) | Fluorierte Sulfonamide als schwer entflammbare Lösungsmittel zum Einsatz in elektrochemischen Zellen | |
JP2014234358A (ja) | カーボネート化合物及びその製造方法 | |
DE10055812A1 (de) | Fluoroalkylphosphat-Salze und deren Verwendung als Leitsalze | |
DE19953638A1 (de) | Fluorierte Sulfonamide als schwer entflammbare Lösungsmittel zum Einsatz in elektrochemischen Zellen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170118 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602015008582 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: B01D0011020000 Ipc: H01M0010540000 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01M 10/54 20060101AFI20171010BHEP Ipc: H01M 10/0568 20100101ALI20171010BHEP Ipc: B01D 11/02 20060101ALI20171010BHEP Ipc: B01D 11/04 20060101ALI20171010BHEP Ipc: H01M 6/52 20060101ALI20171010BHEP |
|
INTG | Intention to grant announced |
Effective date: 20171107 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 977480 Country of ref document: AT Kind code of ref document: T Effective date: 20180315 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015008582 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 4 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180607 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 977480 Country of ref document: AT Kind code of ref document: T Effective date: 20180307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180607 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180608 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015008582 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180709 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
26N | No opposition filed |
Effective date: 20181210 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180630 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180616 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180616 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180616 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180307 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20150616 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180707 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180616 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602015008582 Country of ref document: DE Owner name: SPECIALTY OPERATIONS FRANCE, FR Free format text: FORMER OWNER: RHODIA OPERATIONS, PARIS, FR Ref country code: DE Ref legal event code: R081 Ref document number: 602015008582 Country of ref document: DE Owner name: RHODIA OPERATIONS, FR Free format text: FORMER OWNER: RHODIA OPERATIONS, PARIS, FR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602015008582 Country of ref document: DE Owner name: RHODIA OPERATIONS, FR Free format text: FORMER OWNER: RHODIA OPERATIONS, AUBERVILLIERS, FR Ref country code: DE Ref legal event code: R081 Ref document number: 602015008582 Country of ref document: DE Owner name: SPECIALTY OPERATIONS FRANCE, FR Free format text: FORMER OWNER: RHODIA OPERATIONS, AUBERVILLIERS, FR |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230510 Year of fee payment: 9 Ref country code: FR Payment date: 20230510 Year of fee payment: 9 Ref country code: DE Payment date: 20230502 Year of fee payment: 9 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230624 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230504 Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20240222 AND 20240228 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: PD Owner name: SPECIALTY OPERATIONS FRANCE; FR Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: RHODIA OPERATIONS Effective date: 20240318 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602015008582 Country of ref document: DE Owner name: SPECIALTY OPERATIONS FRANCE, FR Free format text: FORMER OWNER: RHODIA OPERATIONS, LYON, FR |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240515 Year of fee payment: 10 |